Acylformamidine insecticidal and miticidal compounds

ABSTRACT

A composition of matter is described herein which has insecticidal and miticidal activity and methods of use. The composition may be defined by the following generic formula:  wherein R 1  and R 2  are independently methyl or halogen; R 3  is selected from the following groups: ##STR1## R 4  is selected from the group consisting of: alkyl, alkenyl, haloalkyl, haloalkenyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkylthio, alkylamido, arylamido, alkoxyalkyl, alkylthioalkyl, alkylamidoalkyl, arylamidoalkyl, ketoalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkylthiocarbonyl, alkylthiocarbonylalkyl, alkylamidocarbonyl, alkylamidocarbonylalkyl, arylamidocarbonylalkyl, hydroxyalkyl, N-alkylcarbamoylalkyl, N-arylcarbamoylalkyl, cyanoalkyl, thiocyanoalkyl, isothiocyanoalkyl, cyanatoalkyl, phenyl, furyl, thienyl, pyridyl with or without substituents, wherein said substituents can be selected from halogen, alkyl, haloalkyl, alkoxy, carbamyl, nitro, carboxylic acids and their esters, haloalkylcarbamyl; phenylalkyl; phenylhaloalkyl; phenylalkenyl; substituted phenylalkenyl wherein said substituents can be selected from halogen, alkyl, alkoxy; halophenoxy; phenylalkoxy, phenylalkylcarboxyalkyl; phenylcycloalkyl; halophenylalkenoxy; bicycloalkyl with the priviso that when R 4  is alkoxycarbonyl, alkylthiocarbonyl or alkylamidocarbonyl R 3  can only be ##STR2## X=oxygen or sulfur; R 5  and R 6  are independently alkyl, haloalkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, alkylamido and arylamido.

This is a division of application Ser. No. 834,256, filed Sept. 12, 1977now U.S. Pat. No. 4,130,662, which is a division of application Ser. No.666,520, filed Mar. 12, 1976, now U.S. Pat. No. 4,056,570, which is adivision of application Ser. No. 575,313, filed May 7, 1975, now U.S.Pat. No. 3,962,305, which is a division of application Ser. No. 439,507,filed Feb. 4, 1974, now abandoned.

BACKGROUND OF THE INVENTION

Among the many insecticidal and miticidal compounds available, varioussubstituted formamidine compounds have shown such insecticidal andmiticidal activity. Specific examples thereof and methods of use arethose described in U.S. Pat. Nos. 3,502,720 and 3,378,437.

BRIEF DESCRIPTION OF THE INVENTION

It has been discovered that certain acylformamidine compounds are usefulas insecticidal and miticidal compounds. These acylformamidine compoundsmay be defined by the following generic formula: ##STR3## wherein R₁ andR₂ are independently methyl or halogen; R₃ is selected from thefollowing groups: ##STR4## R₄ is selected from the group consisting ofalkyl, alkenyl, haloalkyl, haloalkenyl, cycloalkyl, cycloalkylalkyl,alkoxy, alkylthio, alkylamido, arylamido, alkoxycarbonyl,alkoxycarbonylalkyl, alkylthiocarbonyl, alkylthiocarbonylalkyl,alkylamidocarbonyl, alkylamidocarbonylalkyl, arylamidocarbonylalkyl,alkoxyalkyl, alkylthioalkyl, alkylamidoalkyl, arylamidoalkyl, ketoalkyl,hydroxyalkyl, N-alkylcarbamoylalkyl, N-arylcarbamoylalkyl, cyanoalkyl,thiocyanoalkyl, isothiocyanoalkyl, cyanatoalkyl, phenyl, furyl, thienyl,pyridyl, with or without substituents, wherein said substituents can beselected from halogen, alkyl, haloalkyl, alkoxy, carbamyl, nitro,carboxylic acids and their esters, haloalkylcarbamyl; phenylalkyl;phenylhaloalkyl; phenylalkenyl; substituted phenylalkenyl wherein saidsubstituents can be selected from halogen, alkyl, alkoxy, halophenoxy;phenylalkoxy, phenylalkylcarboxyalkyl; phenylcycloalkyl;halophenylalkenoxy; bicycloalkyl; with the proviso that when R₄ isalkoxycarbonyl, alkylthiocarbonyl or alkylamidocarbonyl, R₃ can only be##STR5## X=oxygen or sulfur; R₅ and R₆ are independently alkyl,haloalkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, alkylamido,arylamido.

DETAILED DESCRIPTION OF THE INVENTION

In the practice of the present invention, the compounds of the presentinvention are manufactured by reacting the properly selected 2, 4disubstituted aniline with an alkyl orthoformate and then reacting theresulting alkylformimidate with methyl amine to obtain the 1 methyl 3disubstituted phenyl formamidine which in turn is reacted with anacylating agent such as an acyl halide, an acyl anhydride or anisocyanate to produce the desired acylformamidine as is shown in theexamples herein.

After the compounds of the present invention are formed, they can beapplied to the habitat in an effective amount to control respectivemites and insects.

The following examples illustrate the merits of the present invention:

EXAMPLE 11-(2'-methyl-4'-chlorophenyl)-3-methyl-3-methylthiolcarbonylformamidine

Into a round-bottom flask, fitted with a mechanical stirrer, was placed1.8 g (0.01 mole) 1-(2'-methyl-4'-chlorophenyl)-3-methylformamidine, 25ml CH₂ Cl₂ and 1.0 g (0.01 mole) triethylamine. The mixture was thencooled in an ice water bath. 1.1 g (0.01 mole) methyl chloro thioformatein 10 ml CH₂ Cl₂ were slowly added dropwise and the mixture stirred atroom temperature for one hour. The reaction mixture was washed twicewith water, dried over magnesium sulfate, filtered and stripped. Productyield was 2.4 g of an oil (N_(D) ³⁰ 1.5960). Structure was confirmed byN.M.R.

EXAMPLE 2 1-(2'-methyl-4'-chlorophenyl)-3-methyl-3 propionylformamidine

Into a round-bottom flask fitted with stirrer using the same procedureas Example 1, was added 1.8 g (0.01 mole)1-(2'-methyl-4'-chlorophenyl)-3-methylformamidine, 25 ml CH₂ Cl₂ and 1.0g (0.01 mole) triethylamine. The mixture was cooled in an ice water bathand 0.92 g (0.01 mole) propionyl chloride in 10 ml CH₂ Cl₂ was addedslowly, dropwise. The remainder of the procedure is as in Example 1above and yielded 1.7 g of solid product having a low melting point.Structure confirmation was by N.M.R.

EXAMPLE 31-(2'-methyl-4'-chlorophenyl)-3-methyl-3-methylcarboxyformamidine

Into a round-bottom flask fitted with stirrer were placed 1.8 g (0.01mole) 1-(2'-methyl-4'-chlorophenyl)-3-methylformamidine, 25 ml CH₂ Cl₂and 1.0 g triethylamine. The mixture was cooled in an ice-water bath and0.94 g (0.01 mole) methyl chloroformate in 10 ml CH₂ Cl₂ were addeddropwise. The mixture was maintained and stirred at room temperature forone hour. The reaction mixture was washed twice with water and driedover magnesium sulfate (MgSO₄), filtered and stripped. The reactionyielded 1.7 g of an oil (N_(D) ³⁰ 1.5622). Structure confirmation was byN.M.R.

EXAMPLE 41-(2'-methyl-4'-chlorophenyl)-3-methyl-3-i-butylthiocarbonylformamidine

Into a round-bottom flask fitted with a stirrer were added 1.8 g (0.01mole) 1-(2'-methyl-4'-chlorophenyl)-3-methylformamidine, 25 ml CH₂ Cl₂and 1.0 g (0.01 mole) triethylamine. The mixture was cooled in anice-water bath and 1.52 g (0.01 mole) i-butylchlorothioformate in 10 mlCH₂ Cl₂ was added dropwise. The mixture was held at room temperature andstirred for one hour. The reaction mixture was washed twice with waterand dried over MgSO₄, filtered and stripped. The reaction yielded 2.9 gof an oil (N_(D) ³⁰ 1.5638). Structure confirmation was by N.M.R.

EXAMPLE 51-(2'-methyl-4'-chlorophenyl)-3-methyl-3-methylsuccinylformamidine

Into a round-bottom flask fitted with stirrer was placed 1.8 g (0.01mole) 1-(2'-methyl-4'-chlorophenyl)-3-methylformamidine, 25 ml CH₂ Cl₂and 1.0 g triethylamine. The mixture was cooled in an ice-water bath and1.5 g (0.01 mole) 3-carboxymethyl propionyl chloride in 10 ml CH₂ Cl₂was added. The mixture was stirred at room temperature for one hour. Thereaction mixture was washed twice with water and dried over MgSO₄,filtered and stripped. Product yield was 2.3 g of a semi-solid.Structure confirmation was by N.M.R.

EXAMPLE 6 1-(2'-methyl-4'-chlorophenyl)-3-methyl-3-methylthiocarbamylformamidine

Into a round-bottom flask fitted with stirrer, was placed 1.8 g (0.01mole) 1-(2'-methyl-4'-chlorophenyl)-3-methylformamidine, 25 ml benzene,0.73 g (0.01 mole) methylisothiocyanate plus two drops of triethylamine.The mixture was refluxed for two hours, cooled and evaporated. Thereaction yielded 2.5 g of a solid, melting at 68°-70° C. Structureconfirmation was by N.M.R.

EXAMPLE 71-(2'-methyl-4'-chlorophenyl)-3-methyl-3-dichloroacetylformamidine

The procedure was the same as in Example 3 above, with the exceptionthat 1.47 g (0.01 mole) dichloroacetyl chloride was used in place of themethylchloroformate. Product yield was 2.2 g of a semi-solid. Structureconfirmation was by N.M.R.

EXAMPLE 81-(2'-methyl-4'-chlorophenyl)-3-methyl-3-methylacrylformamidine

Procedure was the same as in Example 3 above, with the exception that1.04 g (0.01 mole) methacryl chloride was used in place ofmethylchloroformate. The reaction yielded 2.3 g of an oil (N_(D) ³⁰1.5684). Structure confirmation was by N.M.R.

EXAMPLE 9 1-(2'-methyl-4'-chlorophenyl)-3-methyl-3-trifluoroacetylformamidine

1.8 g (0.01 mole) 1-(2'-methyl-4'-chlorophenyl)-3-methylformamidine weredissolved in 15 ml CH₂ Cl₂ and cooled in an ice-water bath. 2.1 g (0.01mole) trifluoroaceticanhydride in 10 ml CH₂ Cl₂ were slowly addeddropwise to the flask, and stirred at room temperature for one hour. Thereaction mixture was washed with 10% NaHCO₃, dried over MgSO₄, filteredand stripped. The reaction yielded 1.9 g of an oil (N_(D) ³⁰ 1.5182).Structure confirmation was by N.M.R.

EXAMPLE 101-(2'-methyl-4'-chlorophenyl)-3-methyl-3-phenylthiocarbamylformamidine

The procedure was the same as in Example 6 above, with the exceptionthat 1.35 g (0.01 mole) phenylisothiocyanate was used in place of methylisothiocyanate. The reaction yielded 3.1 g of a low-melting material.Structure confirmation was by N.M.R.

Other compounds can be prepared in an analogous manner starting with theappropriate materials as outlined above. Following is a table ofcompounds representative of those embodied in the present invention.Compound numbers have been assigned to them and are used foridentification throughout the balance of this specification.

                  TABLE I                                                         ______________________________________                                         ##STR6##                                                                     Compound                                                                      Number  R.sub.1 R.sub.2  R.sub.3                                              ______________________________________                                        1       Cl      CH.sub.3                                                                                ##STR7##                                            2       Cl      CH.sub.3                                                                                ##STR8##                                            3       Cl      CH.sub.3                                                                                ##STR9##                                            4       Cl      CH.sub.3                                                                                ##STR10##                                           5       Cl      CH.sub.3                                                                                ##STR11##                                           6       Cl      CH.sub.3                                                                                ##STR12##                                           7       Cl      CH.sub.3                                                                                ##STR13##                                           8       Cl      CH.sub.3                                                                                ##STR14##                                           9       Cl      CH.sub.3                                                                                ##STR15##                                           10      Cl      CH.sub.3                                                                                ##STR16##                                           11      Cl      CH.sub.3                                                                                ##STR17##                                           12      Cl      CH.sub.3                                                                                ##STR18##                                           13      Cl      CH.sub.3                                                                                ##STR19##                                           14      Cl      CH.sub.3                                                                                ##STR20##                                           15      Cl      CH.sub.3                                                                                ##STR21##                                           16      Cl      CH.sub.3                                                                                ##STR22##                                           17      Cl      CH.sub.3                                                                                ##STR23##                                           18      Cl      CH.sub.3                                                                                ##STR24##                                           19      Cl      CH.sub.3                                                                                ##STR25##                                           20      Cl      CH.sub.3                                                                                ##STR26##                                           21      Cl      CH.sub.3                                                                                ##STR27##                                           22      Cl      CH.sub.3                                                                                ##STR28##                                           23      Cl      CH.sub.3                                                                                ##STR29##                                           24      Cl      CH.sub.3                                                                                ##STR30##                                           25      Cl      CH.sub.3                                                                                ##STR31##                                           26      Cl      CH.sub.3                                                                                ##STR32##                                           27      Cl      CH.sub.3                                                                                ##STR33##                                           28      Cl      CH.sub.3 SO.sub.2 CH.sub.3                                    29      Cl      CH.sub.3 SO.sub.2 -i-C.sub.4 H.sub.9                          30      Cl      CH.sub.3                                                                                ##STR34##                                           31      Cl      CH.sub.3                                                                                ##STR35##                                           32      Cl      CH.sub.3                                                                                ##STR36##                                           33      Cl      CH.sub.3                                                                                ##STR37##                                           34      Cl      CH.sub.3                                                                                ##STR38##                                           35      Cl      CH.sub.3                                                                                ##STR39##                                           36      Cl      CH.sub.3                                                                                ##STR40##                                           37      Cl      CH.sub.3                                                                                ##STR41##                                           38      Cl      CH.sub.3                                                                                ##STR42##                                           39      Cl      CH.sub.3                                                                                ##STR43##                                           40      Cl      CH.sub.3                                                                                ##STR44##                                           41      Cl      CH.sub.3                                                                                ##STR45##                                           42      Cl      CH.sub.3                                                                                ##STR46##                                           43      Cl      CH.sub.3                                                                                ##STR47##                                           44      Cl      CH.sub.3                                                                                ##STR48##                                           45      Cl      CH.sub.3                                                                                ##STR49##                                           ______________________________________                                    

Insecticidal activity of the above compounds were evaluated for efficacyon various insect species as follows:

I. Salt-marsh Caterpillar [Estigmene acrea (Drury)] A. Leaf Dip Assay toDetermine Efficacy Against First Instar Salt-Marsh Caterpillar Larvae

Kidney bean leaves are dipped in a 50--50 acetone-water solution of thetest chemical. When the leaves have dried, egg masses of the salt-marshcaterpillars are placed on the leaf surface. Mortality of the newlyhatched larvae is determined after one week. Test concentrations rangefrom 0.05% down to that at which approximately 50% of the larvae aredead.

B. Ovicidal Screening Procedure

Egg masses of the salt-marsh caterpillar are dipped in acetone solutionsof the test chemicals and placed in petri dishes containing a portion oflarval rearing medium. Efficacy is determined after seven days byobserving the number of newly emerged larvae. Test concentrations rangefrom 0.05% down to that at which approximately 50% of the eggs do nothatch.

II. Black Bean Aphid [Aphis fabae (Scop.)]

Nasturtium Tropaeolum sp.) plants, approximately 2-3 inches tall, aretransplanted into sandy loam soil in 3-inch clay pots and infested with50-75 aphids of mixed ages. Twenty-four hours later they are sprayed, tothe point of runoff, with aqueous suspensions of the toxicant. Thesuspensions are prepared by diluting aliquots of the toxicant, dissolvedin an appropriate solvent, with water to which has been added 0.0002% ofa conventional wetting agent such as polyoxy-ethylene sorbitanmonolaurate ether of alkylated phenol blended with organic sulfonate.Test concentrations ranged from 0.05% to that at which 50% mortality isobtained. Mortality is recorded after 48 hours and the LD-50 values areexpressed as percent active ingredient in the aqueous suspensions.

III. Two-Spotted Mite [Tetranychus urticae (Koch)]

Pinto Beans (Phaseolus sp.) plants, approximately 2-3 inches tall, aretransplanted into sandy loam soil in 3-inch clay pots and infested with50-75 mites of mixed ages. Twenty-four hours later they are sprayed, tothe point of runoff, with aqueous suspensions of the toxicant. Thesuspensions are prepared as in previously described tests (I and II).Test concentrations ranged from 0.05% to that at which 50% mortality isobtained. Mortality of adults, nymphs and eggs is recorded after 7 daysand the LD-50 values are expressed as percent active ingredient in theaqueous suspensions.

IV. Systemic Tests A. Salt-marsh Caterpillar

Aliquots of toxicant dissolved in an appropriate solvent are diluted inwater and placed in glass bottles. Concentrations of active ingredientrange from 10 ppm to that at which 50% mortality is obtained. Kidneybeans (Phaseolus vulgaris), supported by cotton plugs, are inserted intothe solution so that the roots and major portion of the stem arecompletely immersed. Masses of caterpillar eggs which are nearly readyto hatch are fastened to the bean leaves. One week later mortality ofthe newly hatched larvae is recorded. LD-50 values are expressed as ppmof toxicant in the aqueous suspensions.

B. Two-Spotted Mite

Preparation of the test solution and concentrations is the same as forthe Salt-marsh Caterpillar test (IV-A). Pinto bean (Phaseolus sp.)plants with expanded primary leaves are placed in the solution so thatthe roots and major portions of the stem are completely immersed.Immediately after, the leaves are infested with 75-100 mites of variousages. Mortality of adults, nymphs and eggs is recorded after one week,and LD-50 values are expressed as ppm of toxicant in the aqueoussuspensions.

The results of the above test procedures indicate in Table II theeffective concentration at which LD-50 control effect was achieved onthe various species of insects.

                                      TABLE II                                    __________________________________________________________________________               SMC                                                                           Leaf            2SM                                                Compound                                                                            BA   Dip   Ovicide                                                                            SYS  Pe  Eggs                                                                              SYS                                        Number                                                                              %    %     %    ppm  %   %   ppm                                        __________________________________________________________________________    1     .03        .1   3    .08 .02 >10                                        2     .01        .01       .04 .01                                            3     .005       .01  .1   .04 .005                                                                               10                                        4     .003       .005 3    .04 .006                                                                              >10                                        5     .01        >.1  .5   .08 .02  10                                        6     .05  .0003 .005 8    >.05                                                                              .05 --                                         7     .001 .0008 .0008                                                                              1    .03 >.05                                                                              >10                                        8     .05  .0005 .008 .2   .005                                                                              >.03                                                                              >10                                        9     .003 .0003 .008 .5   .01 .03 >10                                        10    .001 .0003 .0008                                                                              .3   .01 .03 >10                                        11    >.05 .005  >.05 3    >.05                                                                              >.05                                                                              --                                         12    .003 .001  .03  .3   .005                                                                              >.05                                                                              >10                                        13    .003 .005  .03  .5   .005                                                                              >.05                                                                              >10                                        14    .0008                                                                              .0003 .003 .1   .008                                                                              >.05                                                                              >10                                        15    .05  .0005 .005 .3   .01 >.05                                                                              >10                                        16    .003 .0008 .005 .3   .01 > .05                                                                             >10                                        17    .003 .0008 .005 .08  .03 >.05                                                                              >10                                        18    .05  .0001 .03  1    .005                                                                              .03 >10                                        19    .003 .0005 .03  .3   .03 .03 >10                                        20    .001 .0008 .01  .5   .01 .03 >10                                        21    >.05 >.05  >.05 >10  >.05                                                                              >.05                                                                              --                                         22    >.05 .03   >.05 >10  >.05                                                                              >.05                                                                              --                                         23    .003 .003  .03  .3   .01 >.05                                                                               10                                        24    .005 .00008                                                                              .01  .3   .01 >.05                                                                              >10                                        25    >.05 >.05  >.05 >10  >.05                                                                              >.05                                                                              --                                         26    .03  .008  >.05 3    .03 >.05                                                                              >10                                        27    .003 .0008 .01  .1   .005                                                                              >.05                                                                              >10                                        28    .05  .0008 >.05 3    >.05                                                                              >.05                                                                              >10                                        29    .005 .008  .03  3    >.05                                                                              >.05                                                                              >10                                        30    >.05 .003  >.05 .8   .03 >.05                                                                              >10                                        31    .001 .0008 .03  .3   .01 >.05                                                                              >10                                        32    .0008                                                                              .01   .003 .8   .03 >.05                                                                              >10                                        33    .003 .005  .03  >10  .03 >.05                                                                              >10                                        34    .05  .05   >.05 3    > .05                                                                             >.05                                                                              >10                                        35    .001 .0003 >.05 .3   .03 .05 >10                                        36    .01  .0005 >.05 .3   .03 >.05                                                                              >10                                        37    .003 .00008                                                                              .003 .03  .01 >.05                                                                              >10                                        38    .005 .0003 .05  .3   .01 .03                                            39    .003 .0003 .01  .08  .01 >.05                                           40    =.05 .0008 >.05 .3   .03 >.05                                           41    .01  .00008                                                                              .01  .1   .01 >.05                                           42    .01  .0008 .05  .08  .01 .03                                            43    >.05 .0008 >.05 5    .03 .03                                            44    .03  .0001 .008 .8   .03 .05                                            45    .03  .001  .03  .8   .01 .03                                            __________________________________________________________________________     SMC = Saltmarsh Caterpillar                                                   SYS = Systemic                                                                2SM = Twospotted Mite                                                         BA = Bean Aphid                                                               > greater than                                                                < less than                                                                   Pe = Postembryonic                                                       

The compounds of this invention are generally embodied into a formsuitable for convenient application. For example, the compounds can beembodied into pesticidal compositions which are provided in the form ofemulsion, suspensions, solutions, dust and aerosol sprays. In general,such compositions will contain, in addition to the active compound, theadjuvants which are normally found in pesticide preparations. In thesecompositions, the active compounds of this invention can be employed asa sole pesticide component or they can be used in a mixture with othercompounds having similar utility. The pesticide compositions of thisinvention can contain as adjuvants organic solvents such as sesame oil;xylene solvents; heavy petroleum, etc; water; emulsifying agents;surface active agents; talc; pyrophyllite; diatamite; gypsum; clays;propellents; such as dichlorodifluormethane, etc. If desired, however,the active compounds can be applied directly to feedstuffs, seeds, etc.upon which these pests feed. When applied in such a manner, it will beadvantageous to use a compound which is not volatile. In connection withthe activity of the presently disclosed pesticidal compounds, it shouldbe fully understood that it is not necessary that they be active assuch. The purposes of this invention will be fully served to thecompound as rendered active by external influences, such as light or bysome physiological action which occurs when the compound is ingestedinto the body of the pests.

The precise manner in which the pesticidal composition of this inventionare used in any particular instance, will be readily apparent to aperson skilled in the art. Generally, the active pesticide compound willbe embodied in the form of a liquid composition. For example, anemulsion, suspension or aerosol spray. While the concentration of theactive pesticide in the present compositions can vary within rather widelimits, ordinarily the pesticide compound will comprise not more thanabout 15.0% by weight of the pesticidal composition. Preferably,however, the pesticide compositions of this invention will be in theform of solutions or suspensions containing from about 0.1 to about 1.0%by weight of the active pesticide compound.

What is claimed is:
 1. A method of controlling insects and mitesconsisting of applying thereto or to the habitat thereof an insecticidalor miticidal effective amount of compounds having the formula: ##STR50##wherein R₁ and R₂ are independently methyl or halogen; R₃ is ##STR51##and R₄ is alkylthio.
 2. The method of claim 1 wherein R₁ is Cl; R₂ isCH₃ and R₃ is ##STR52##
 3. The method of claim 1 wherein R₁ is Cl; R₂ isCH₃ and R₃ is ##STR53##
 4. The method of claim 1 wherein R₁ is Cl; R₂ isCH₃ and R₃ is ##STR54##
 5. The method of claim 1 wherein R₁ is Cl; R₂ isCH₃ and R₃ is ##STR55##
 6. The method of claim 1 wherein R₁ is Cl; R₂ isCH₃ and R₃ is ##STR56##
 7. The method of claim 1 wherein R₁ is Cl; R₂ isCH₃ and R₃ is ##STR57##
 8. The method of claim 1 wherein R₁ is Cl; R₂ isCH₃ and R₃ is ##STR58##
 9. The method of claim 1 wherein R₁ is Cl; R₂ isCH₃ and R₃ is ##STR59##
 10. The method of controlling insects and mitesconsisting of applying thereto or to the habitat thereof an insecticidalor miticidal effective amount of the compound having the formula##STR60## wherein R₁ is Cl; R₂ is CH₃ and R₃ is ##STR61##
 11. The methodof controlling insects and mites consisting of applying thereto or tothe habitat thereof an insecticidal or miticidal effective amount of thecompound having the formula ##STR62## wherein R₁ is Cl; R₂ is CH₃ and R₃is ##STR63##